Triazine herbicides



United States Patent O 3,538,093 TRIAZINE HERBICIDES Paul James Mason, Chester, and Harry Edwards Ulmer,

Hopewell, Va., assignors to Allied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Original application Sept. 13, 1968, Ser. No. 759,798, now Patent No. 3,494,759. Divided and this application Sept. 4, 1969, Ser. No. 872,798 Int. Cl. C07d 55/20 US. Cl. 260-249.8 3 Claims ABSTRACT OF THE DISCLOSURE 2-chloro 4 al-kylamino-6- (fluoro-2-hydroxyisopropylamino)-s-triazines are prepared by reacting 2-amino-4- chloro-6-alkylamino-s-triazine with an appropriately fiuorinated acetone. The products are useful as herbicides.

REFERENCE TO RELATED APPLICATION This application is a divisional application of application Ser. No. 759,798, Sept. 13, 1968, now US. Pat. No. 3,494,759.

BACKGROUND OF THE INVENTION This invention relates to novel triazine compounds; in particular, it relates to 2-chloro-4-alkylamino-6- (fluoro-2 hydroxyisopropylamino)-s-triazines which are herbicidal agents.

Over the past few years a large number of chemical herbicides have been placed on the market, but despite the increasing number of herbicides there remain problems for which none or few herbicides are appropriate. For example, nonselective herbicides are available which, when used for post-emergence, will produce high kills of all vegetation; selective herbicides are available which will attack dicotyledonous or monocotyledonous plants but which also cause a high percent of crop injury. There are very few compounds available which are so selective that they will attack all forms of vegetation with the exception of one crop and, accordingly, there is a great need in the art for such a herbicide. This need may be shown by the fact that previously, in order to destroy all vegetation except one crop, it was necessary to employ at least two separate herbicide,s a method which would make such a procedure economically and commercially impractical.

SUMMARY OF THE INVENTION The novel triazines of the instant invention are those of the formula wherein X and X are each selected from the group consisting of fluorine, chlorine and hydrogen, and R is alkyl containing up to 4 carbon atoms. These compounds are highly selective herbicides.

DETAILED DESCRIPTION OF THE INVENTION The instant substituted triazines are synthesized by Patented Nov. 3, 1970 reacting 2-amino-4-chloro-6-alky1amino-s-triazine with a fiuoroacetone according to the sequence.

wherein X, X and R are as aforesaid. An excess of the acetone reagent is preferred for improved yields, although equimolar quantities may be used in the mixture. The reaction is conducted in a reaction-inert solvent such as acetone and the like; preferred solvents include ketones such as acetone.

The recation mixture is normally allowed to react with agitation at ambient temperatures of about 15-35 C. and at atmospheric pressure, although higher temperatures and pressures may be used. The mixture is allowed to react for 8-24 hours. After the completion of the reaction, the solvent is removed under reduced pressure to produce the product, normally a solid, which may be purified by recrystallization from methyl ethyl ketone.

2-amino-4-chloro-6-alkylamino-s-triazine, used as substrate in this synthetic procedure, may be obtained by methods taught in the prior art, for example, Pearlman and Banks, 1. Am. Chem. Soc., 70, 3726-3728 (1948). The various fluoro and chlorofluoroacetones used as substrate are available by methods taught by Cyril Woolf, Kirk- Othmer Encyclopedia of Chemical Technology, Second edtion, vol. 9, pages 754-767, Interscience Publishers, 1966.

The instant compounds have been found to be unexpectedly effective herbicides in that they are very harmful to plants normally considered undesirable, such as grass and broadleafed weeds, while being harmless toward such plants as corn. 2-chloro-4-ethylamino-6-(2-hydroxyl,l,1,3,3,3-hexafluoroisopropylamino)-s-triazine is the preferred compound for this purpose.

Normally, the instant compounds will be used as the active ingredient in an herbicidal composition, although they might also be used without a carrier. Various diluents and carriers may be employed and the percent of active ingredient may be varied. Although compositions with less than about .25 by Weight of active ingredient may be used, it is preferable to use compositions containing at least about .5 0% of active ingredient because otherwise the amount of carrier becomes excessively large. Activity increases with the concentration of active ingredient, which may be 10, 50, or even higher.

The amount of composition which is applied for effective herbicidal action is dependent upon considerations such as the type of undesirable plant to be killed, the density of undesirable plants, and soil and climatic conditions. Usually, sufficient composition will be applied to provide about 1-10 pounds of active ingredient per acre.

The instant herbicidal compositions may be in the form of a solution, with the solvent being selected from acetone,

methanol and the like. These solutions can be applied to the plants in a direct manner such as by spraying, sprinkling, drenching, etc. Liquid suspensions can also be applied in this manner, with the dispersant selected from liquids such as water and the like.

Application can also be achieved by dusting a powder in which the active ingredient is dispersed. Suitable carriers include finely powdered material such as clay, fullers earth and tale.

The instant compounds may constitute the sole active ingredient in the herbicidal compositions, but they might be effectively used in combination with other active ingredients, such as other herbicides, insecticides and other plant treating agents.

Inasmuch as the instant compounds are only sparingly soluble in water, it is often convenient to utilize them in the form of their water-soluble salts, for example the hydrochloride salt.

The following examples are provided to more fully illustrate the instant invention. They are provided for illustrative purposes only and are not to be construed as limiting the scope of the instant invention, which is defined by the appended claims.

EXAMPLE I 2-chloro-4-ethylamino-6-(2-hydroxy-1,1,1,3,3 ,3-hexafluoroisopropfylamino -s-triazine 2 amino 4-chloro-6-ethylamino-s-triazine grams) was mixed in a flask with 500 ml. acetone. Hexafluoroacetone (54 grams) was bubbled into the mixture and the resulting mixture was stirred at about 22-37 C. for 24 hours. The solvent was then evaporated under reduced pressure and the resulting liquid was filtered. A solid product gradually crystallized from the filtrate to afford the desired product, M.P. 152 C.

EXAMPLE II The procedure of Example I is repeated wherein appropriate alkylaminotriazines and substituted acetones are employed to afford the following products:

2-chloro-4-rnethylamino-6- 2-hydroxyl ,3-difluoroisopropylamino -s-triazine 2-chloro-4-methylamiuo-6- (2-hydroxy-l ,3-difluoro- 1,3-dich1oroisopropylamino)-s-triazine 2-chloro-4-ethylamino-6-(Z-hydroxy-l,1,3,3-tetrafluoroisopropylamino) -s-triazine 2-chloro-4-methylamin0-6- (2-hydroxy-1,1,3 ,3-tetrafluoro-l,3-dichloroisopropylamino)-s-triazine 2 chloro 4 isopropylamino-6-(2-hydroxy-1,3-difluoro- 1,3-dichloroisopropylamino)-s-triazine 2-chloro-4-n-butylamino-6-(Z-hydroxy-1,3-difluoroisopropylamino) -s-triazine 2 chloro 4-n-butylamino-6-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropylamino)-s-triazine 2 chloro 4-methylamino-6-(2-hydroxy-l,1,1,3,3,3-hexafluoroisopropylamino) -s-triazine EXAMPLE III Herbicidal activity The following crop species and weed species were platend in metal flats (12 X 8.5 x 4 inches) in greenhouse potting soil containing one-third mixed clay and sand, one-third mushroom soil, and one-third peat moss. The pH of the soil was 6.8-7.2.

Crop species:

Corn Oats Weed species:

Mustard Yellow Foxtail Crabgrass Buckwheat Morning Glory Each fiat received a volume of spray equal to 50 gallons per acre of an acetone solution of 2-chloro-4-ethylamino- 6 (2 hydroxy 1,1,1,3,3,3-hexafluoroisopropylamino) -striazine. The concentration of the solution was adjusted to provide application of 2, 4 and 10 pounds of active ingredient per acre. Immediately after spraying, the test flats were placed in aluminum trays and where irrigated until the surface of the soil in the flat was uniformly moist (at field capacity). Additional subirrigation was provided as needed to maintain moisture. No surface irrigation was applied.

The flats were sprayed within one day after seeding in preemergence tests, and 8-10 days after seeding the postemergence tests. Results were observed 14 days after spraying.

The eflect of the herbicide was evaluated in terms of the injury rating index scale, ranging from 0 to 10 as follows:

No apparent injury 0 Slight injury 1,2,3 Moderate injury 4,5,6 Severe injury (plants will die) 7,8,9

Plants were dead 10 An injury rating of 3 is the maximum tolerated for crops and a rating of 7 is the minimum acceptable on weed plants.

1 10 pounds of active ingredient per acre. 2 4 pounds of active ingredient per acre. 3 2 pounds of active ingredient per acre.

What is claimed is: 1. A compound of the formula wherein X and X are each selected from the group consisting of fluorine, chlorine and hydrogen, and R is alkyl containing up to 4 carbon atoms.

2. A compound of claim 1 wherein X and X are each fluorine.

3. The compound of claim 1 wherein X and X are each fluorine and R is ethyl.

References Cited UNITED STATES PATENTS 2,891,855 6/1959 Gysin et al 260249.8 XR 3,346,576 10/ 1967 Steinbrunn et al. 260249.8

HENRY R. JILES, Primary Examiner I. M. FORD, Assistant Examiner U.S. c1. X.R. 

